Substituted oxazoljbines and process



United States Patent SUBSTITUTED OXAZOLIDINES AND PROCESS FOR PREPARING THE SAME Rudi Riitz, Columbus, Ohio, assignor to Bohme Fettchemie G. m. b. I-L, Dusseldorf, Germany No Drawing. Application June 24, 1953, Serial No. 363,930

Claims priority, application Germany August 13, 1952 8 Claims. (Cl. 260-4407) in which R stands for an alkyl, aryl, aralkyl or cycloalkyl radical and R or R for hydrogen or a hydrocarbon radical. If R, R or R stand for a hydrocarbon radical, they may be interrupted by hetero atoms or hetero atom groups; or they may have substituents in the hydrocarbon chain.

The reaction may be carried out at temperatures below 100 C., preferably at room temperature, and is advantageously allowed to proceed in an inditferentsolvent free from water, e. g. benzene, toluene, tetrahydro naphthalene, decahydro naphthalene, chlorinated hydrocarbons, or the like. Apparently, a chloromethyl ether is first formed as an intermediate, which immediately continues to react with ring formation thus forming the oxazolidine.

As starting materials for the process according to the present invention I may use for instance the following oxyalkylated sulfonamides: N-(B-oxyethyl)-butanesulfonamide, N-(B-oxyethyD-dodecane sulfonamide, N-(B- oxyethyl) 4 toluene sulfonamide, N (,3 oxyethyl) -4- alkylbenzene sulfonamide, N-(/3-oxyethyl)-4-nitrobenzene sulfonamide, N,N'-di( 3-oxyethyl) -1,3-benzenedisulfamide, N-(fi-y-dioxypropyl)-dodecyl benzene sulfonamide etc.

As oxo compounds or substances giving off oxo compounds I may use primarily formaldehyde, paraformaldehyde, trioxymethylene, hexamethylenetetramine, and the like. Other compounds to be used are: acetaldehyde, benzaldehyde, acetone, acetophenone, cyclohexanone etc. As hydrogen halide I use primarily hydrogen chloride, but other hydrogen halides may likewise be used.

The novel substituted oxazolidines according to the present invention are compounds difficultly soluble in water, but which are readily soluble in organic solvents. In acid solution, they are decomposed with re-formation of the N-(fi-oxyalkyl) sulfonamides and the 0x0 compounds used in their preparation; in alkaline solutions they are stable.

The novel compounds may be used as intermediates in the preparation of pesticides, textile finishing agents, and pharmaceuticals. They exhibit disinfectant properties; when they contain higher molecular hydrocarbons, they have the properties of softeners for plastics.

While it was known that N-alkylated and N-arylated F 2,722,531 Patented Nov. 1, 1955 oxazolidines may be obtained by ring formation when reacting N-alkylated or N-arylated oxyethyl amines with formaldehyde in alkaline aqueous solutions, the reaction cannot be carried out with N-(fl-oxyalkyl) sulfonamides. It was therefore unexpected that the reaction could 'be carried out under the conditions applied according to the present invention. a

The invention will now be described more fully in a number of examples, but it should be understood that these are given by way of illustration and not of limitation and that many variations in the starting materials and the quantities reacted may be made without departing from the spirit of the invention.

Example 1 21.5 grams N-(p-oxyethyl)-4-toluene sulfonamide (-91 mol) and 3.3 grams paraformaldehyde are suspended in 250 cc. dry benzene, and dry hydrogenchloride is introduced into the suspension while stirring. The reactants are dissolved and water is formed as a separate layer. This aqueous layer is separated from the benzene layer and the dissolved hydrogenchloride driven off by the introduction of a dry air current. The solvent is dried with calciumchloride and thereafter distilled in vacuo, leaving an oily residue which, after a while, solidifies in crystalline form. N-(4-toluene sulfonyl)-oxazolidine is obtained in almost quantitive amount. The compound can be dissolved in water and recrystallized therefrom; it has then a melting point of 105-106 C.

Example 2 47 grams N-(fl-oxyethyl)-4-chlorobenzene sulfonamide (Vs mol) and 6.6 g. paraformaldehyde are reacted in 200 cc. dry benzene with introduction of gaseous hydrogen chloride as described in Example 1. After distilling oil the benzene, an oil is obtained which is Washed in water until the reaction is neutral and is then dried in vacuo, whereupon it solidifies in crystalline form. After recrystallization in Water I obtain N-(4- chlorobenzenesulfonyl)-oxazolidine in colorless fine needles of a melting point of 83 to 84 C.

Example 3 12.8 grams N-(fi-oxyethyD-dodecane sulfonamide Example 4 In a similar manner as described above, N-(dodecanesulfonyl)-5-oxymethyl-oxazolidine is obtained in the form of an almost colorless semi-solid mass from 6.46 g. N-(B-y-dioxypropyl)-dodecane sulfonamide (M. P. 109-110" C.) and 0.66 g. paraforrnaldehyde.

Example 5 24.6 g. N-(fi-oxyethyl)-4-nitrobenzene sulfonamide mol), (M. P. 126.5127.5 C.), 3.3 g. paraforrnaldehyde and gaseous hydrogen chloride in benzene solution are converted into N-(4-nitrobenzene-sulfonyl)-oxazolidine in about yield. The clear yellow oil obtained after distilling off the benzene is washed with water until neutral and gradually takes on solid form. After having been dried in vacuo, it can be ground to a fine powder which is recrystallized from a mixture of water and acetone. The thus obtained N-(4-nitrobenzenesulfonyD-oxazolidine is light yellow and melts at about 110 C. after previous sintering.

Example 6 176.5 g. mol) of a N-(fi-oxyethyl)-alkylbenzene sulfonamide obtained from alkylbenzene sulfochloride mixture (mean alkyl chain length C13) and mono-ethanolamine are reacted with 16.5 g. paraformaldehyde in 400 cc. benzene while gaseous hydrogen chloride is introduced. The viscous reaction product remaining after benzene has been distilled in vacuo, is washed to neutral reaction with 10% common salt solution. The product is dissolved in ether and dried with sodiumsulfate. After filtration and removal of the solvent, N-(alkylbenzenesulfonyl)oxazolidine is obtained in form of a clear brown syrup.

What I claim is:

1. A substituted oxazolidine having the formula wherein R represents a radical selected from the group consisting of alkyl having up to 12 carbon atoms, phenyl, chlorophenyl, nitrophenyl and alkylphenyl radicals having up to 13 carbon atoms in the alkyl group, and wherein R and R each represents a radical selected from the group consisting of hydrogen and lower alkyl radicals.

2. As a novel compound a substituted oxazolidine of the formula N-(4-toluene sulfonyl)-oxazolidine.

3. As a novel compound a substituted oxazolidine of the formula N-(4-chlorobenzene sulfonyl)-oxazolidine.

which comprises reacting an N-(fi-oxyalkyl)-sulfonamide having the configuration with an aldehyde having the configuration R"CHO in the presence of a hydrogen halide, wherein R represents a radical selected from the group consisting of alkyl having up to 12 carbon atoms, phenyl, chlorophenyl, nitrophenyl and alkylphenyl radicals having up to 13 carbon atoms in the alkyl group, and wherein R and R each represents a radical selected from the group consisting of hydrogen and lower alkyl radicals.

References Cited in the file of this patent Bergmann: Chem. Reviews, vol. 53, pp. 310-14 (1953).

Read et al.: J. Chem. Soc., vol. 1929, pp. 2305-6. 

1. SUBSTITUTED OXAZOLIDINE HAVING THE FORMULA 